Insecticide



Patented Apr. 18, 1939 um'riao s'm'ras PAT NT OFFEQE I INSECTICIDE NoDrawing. Application September 3, 1937, Serial No. 162,384

16 Claims.

This invention relates to insecticides and has for its particular objectthe provision of an oil readily dispersible in water to form an emulsiontherewith, in which the emulsifier comprises a benzene compound havinginsecticidal qualities not contained in methane derivatives.

The preferred emulsifier to be mixed with a crude oil, or a distillatethereof which has been more or less highly refined by well knowntreatment with sulfuric acid or a selective solvent (e. g., liquidsulfur dioxide) or a combination of these to remove more or less of theunsaturated (phytocidal) hydrocarbons therefrom, comprises additionproducts of hydroxylic derivatives of benzene and its homologues,containing an bydroxyl group directly attached to the benzene nucleus,e. g., phenol, cresol, xylenol, with unsaturated aliphatic acids likeoleicor riclnoleic acid.

Because the chemical structure of such addition products has not beendefinitely ascertained, they are so far not characterized by definitenames and for brevity and convenience they will be designated hereinbroadly as benzene hydroxylic fatty acids, of which specific typesinclude phenol-oleic acid, cresol-ricinoleic acid, xylenol-oleic acid,etc.

In the preparation of such compounds as an emulsifier for oils, thebenzene derivative is caused to react with the unsaturated fatty acid bymixing them in the proportion of their molecular weights, at atemperature above their melting points, as for instance 94 parts byweight of phenol with 282 parts by weight of oleic acid to form theaddition product called phenol-oleic 'acid, and 108 parts by weight ofcresol with 298 parts of ricinoleic acid to form cresol-riclnoleic acid.It should be understood, however, that other ratios of phenol or itshomologues to unsaturated fatty acids are included and that theinvention is not limited to these proportions, though equi-molecularproportions are preferred.

Whereas the reaction between the fatty acid and the phenol homologuetakes place when both constituents are in a fluid state, the minimumtemperature required for the reaction is the melting point of thehomologue of phenol desired to be used, if the melting point of thefatty acid is below that of the homologue of phenol. On the other hand,if the melting point of the fatty acid desired for use is higher thanthat of the homologue of phenol, then obviously it is necessary to use atemperature higher than the melting point of the fatty acid. Forinstance, in order to form the addition product phenol-oleic acid, theminimum temperature required will be F., as the phenol melts at 105 F.;for the formation of phenol-chaulmoogric acid the minimum temperature is155 R, which corresponds to the melting point of chaulmoogric acid.

The following table gives the melting points of several materialssuitable for the preparation of addition products in accordance with theinvention.

Homologues of phenol: 1o

' M. P. F. Phenol 105 .Ortho-cresol 86 Meta-cresol 39 Para-cresol 95 15Xylenol (1,2) (3) 167 Xylenol (1,2) (4) 149 Xylenol (1,3) (2) Xylenol(1,3) (4) 79- Xylenol (1,3) (5) 147-154 Xylenol (1,4) (3) 165 Thymol 111Carvacrol 32 Fatty acids:

Oleic acid 57 Iso-oleic acid 112 Elaidic acid 124 Ricinoleic acid 63Linolic acid 0 Linoleic acid (below) 0 80 Linolenic acid (below) 60Clupanodonic acid (below) 60 Telfairic acid 43 Erucic acid s 92Isolinoleic acid (below) 60 35 Chaulmoogric acid The commerciallyobtainable mixtures of xylenols, which form liquids at ordinarytemperatures, can be used without further purlfie 40 cation for thepreparation of oil soluble addition products similarln efliciency tophenololeic acid, for instance. Likewise, unsaturated fatty acidscontaining impurities may be used. Such impure acids have melting pointswhich 45 vary and which may be considerably below the melting point ofthe pure acids.

The maximum temperature which may suitably be employed is one at whichthere is no appreciable loss of the constituents due to vol- 50atilization. Furthermore, as the temperature is increased there is anoticeable tendency to form esters instead of the desired additionproducts. Temperatures upto 350 F. have been satisfactorily employed inthe manufacture of addition products in accordance with the invention. r

Addition products prepared as described above may readily bedistinguished from ordinary mixtures and from esters. For example,whereas phenol is soluble in either water or glycerol and should beextracted from a mixture of phenol cresol and oleic acid:

PM? My mso- Calculated Oleic ciatiori or Cresylvalues for acid $8501addition oleate a theoretical product K mixture Spec. grav. at

20 C 0. 8984 1. 0354 0. 9315 0. 9003 0. 9363 Refr. index at C l. 4622 l.5398 1. 4818 1. 5047 1. 4836 S p e c. r e i r.

power 0. 6133 0.4237 0. 5173 0. 5547 I 0. 4885 The specific refractivepower is calculated as follows:

Refractive index at 20 C.l

Specific gravity at 20 0.

Such phenol-oleic acid, or other benzene hydroxylic fatty acid, may bemixed with crude petroleum, or a distillate thereof more or less refinedup to the point of containing no phytocidal hydrocarbons, for examplein'the proportion of from about 0.1% to by volume,

- preferably from 0.5 to 5.0% by volume, of the hydrocarbon oil to forman insecticidal spray oil which may be used as is alone when dispersedor emulsified in water for spraying on trees, foliage, fruit etc. insome cases, but in other cases is desirable to be used in combinationwith a spreader or flux, which has the function of spreading the oil ina film of desirable and uniform thickness over the surfaceto be sprayedand causing it to adhere to the same for a desired length of time.

The emulsion formed by the dispersion of the emulsifiable oil in waterin the proportion of from to 10%, the desirable rate being determined bythe season in which the spraying is done, the type of water used inmaking the spray-mixture, the type of insect to be destroyed and theplants to be protected, is of the quickbreaking type, or non-stabletype, in that such emulsion almost instantly resolves itself into itscomponents of oil and water when it is sprayed on plants, letting thewater run 01? the leaves and leaving the insecticidal oil on the plantto form an insecticidal film.

As the described addition products are miscible with hydrocarbon oil inall proportions the invention is not to be limited to the proportionsgiven above but contemplates their use in any proportion. When mixedwith suitable hydrocarbon oil the resultant emulsifiable oil is harmlessto plant life if used in proper dispersion with water; all of which isimportant in the preparation and applicationpf any insecticide. Theseaddition products, without dilution with hydrocarbon or other oil, arevaluable for use as insecticides; and, due to their emulsifyingproperties, can be dispersed in water, with or without the assistance ofspreaders, in proper proportion to render them harmless to plant life.

well as the degreeof adhesion to the plant sur- Water used in thepreparation of the spray mixture will Influence dispersion andfilm-properties, the inclusion of Spreaders, or a flux, has been founddesirable to counteract adverse reactions due to heavy mineralizationand to produce an oil-film utilizing the full insecticidal effect of theoil, which film will contain the correct amount of oil and poison persquare unit of surface covered, without causing injury to the plants.

The spreaders desired are:

(1) 100% soda ash or sodium carbonate (NazCOa), to be used when anespecially fine dispersion of the emulsifiable oil is desired and whenthe water used for dispersion is not very soft. In the average the rateof one pound soda ash for 300 gallons water has been found emcient.

Per cent (2) Soda ash 16.5 Brock clay (a magnesium silicate) 16.5 Sodiummietasilicate, 16.5 Trisodium phosphate 16.5 Powdered skim milk 34.0

This spreader is desirable when the water used for dispersion is ratedhard. The amount of such spreader depends on the degree of hardness ofthe water and also on the degree of dispersion desired and may vary frompound per 300 gallons up to six pounds per 300 gallons or even more.

When preparing a spray mixture, say of 100 gallons volume, the followingprocedure will be found the most efiicient:

(A) Using no spreader: Run into the spray tank 25% or less of the water,add the desirable amount of emulsifiable oil, whichmay or may notcontain an oil soluble insecticide poison, and agitate the mixture untilthe desired degree of dispersion has been obtained, then add the balance('75 gals.) of the water. The spray-mixture is then ready for use,

(13) When a spreader is used: Run into the spray tank 25% (or less) ofthe water, dissolve the desirable amount of spreader, add the desirableamount (say 2 gals.) of the emulsifiable oil, which may or may notcontain an oil soluble insecticide poison, agitate this mixture untilthe desired degree of dispersion has been obtained, and finally add thebalance (75 gals.) of water. The spray-mixture is then ready for use.

In place of the poisons and spreaders above described, aslngle'substance may be added to act as a combined spreader and poison.Such a substance can be lead arsenate, which in the average is used atthe rate of two pounds per 100 gallons of water.

From the above description it will be clear that an emulsifiableinsecticide, non-injurious to plant life when properly dispersed inwater, but sufiiciently toxic to all classes of insects may be obtainedby forming an addition product of, phenol or its homologues withunsaturated fatty acids. 'a crude oil or preferably to a more or lesshighly refined distillate thereof, to obtain a compound easilydispersible in water with and without a In order to control thethickness of the film as face, considering that the mineralization ofthe Such addition product may be added to l" spreader forming anemulsion reverting to the oil and water components thereof substantiallyas quickly as it comes in contact with the point of application so thatan oil-film oi desirable properties will coat the same. Incorporatedtherewith may be a poison of such character as not to be water solublebut to be soluble in the oil whereby an even distribution of the poisonin the oil film may be had.

This application is a continuation-in-part of my copending applicationSerial No. 707,853, filed January 22, 1934.

I claim as my invention:

1. The process of preparing an emulsifier for hydrocarbon oils, whichcomprises: mixing a mono-hydroxylic benzene derivative having itsvolatilization or esterification occurs, to form an addition productunaccompanied by the formation of reaction products differing from. thecomponents of said mixture.

2. The process of preparing an emulsifier for hydrocarbon oils, whichcomprises: mixing a mono-hydroxylic benzene derivative having itshydroxyl directly attached to the benzene ring alone with an unsaturatedfatty acid while at a temperature above the melting point of both andbelow about 350 F. to form an addition product unaccompanied-by theformation of reaction products difiering from. the components of saidmixture.

3. The process of preparing an emulsifier for hydrocarbon oils, whichcomprises: mixing a mono-hydroxylic benzene derivative having itshydroxyl directly attached to the benzene ring alone with anunsaturatecl fatty acid while at a temperature between about 105 F. and350 F.'to form an addition product unaccompanied by the formation ofreaction products difiering from the components of said mixture.

4. The process of preparing an emulsifier for hydrocarbon oils, whichcomprises: mixing a mono-hydroxylic benzene derivative having itshydroxyl directly attached to the benzene ring alone with an unsaturatedfatty acid in the proportion of their molecular weights while at atemperature above the melting. point of both, and below a temperature atwhich substantial volatilization or esterification occurs, to form.

6. The process of preparing an emulsifier for hydrocarbon oils, whichcomprises: mixing a mono-hydroxylic benzene derivative having itshydroxyl directly attached to the benzene ring alone with an unsaturatedfatty acid in the proportion of their molecular weights while at atemperature between about 105 F. and 350 F. to form an addition productunaccompanied by the formation of reaction products differing from thecomponents of saidmixture.

7. The process of preparing an emulsifier for hydrocarbon oils, whichcomprises: mixing a phenol alone with an unsaturated fatty acid while ata temperature above the melting'point of both, and below a temperatureat which substantial volatilization or esterification occurs. to form aphenol-fatty acid addition product alone.

8. The process of preparing an emulsifier for hydrocarbon oils, whichcomprises: mixing a phenol alone with an unsaturated fatty acid while ata temperature between about 105 1. and 350 F. to form a phenol-fattyacid addition product alone.

9. An emulsifier for hydrocarbon oils comprising an addition product ofa mono-hydroxylic benzene derivative having its hydroxyl directlyattached to the benzene ring with an unsaturated fatty acid.

10. An emulsifier for hydrocarbon oils comprising: phenololeic acid.

11. An emulsifier for hydrocarbon oils comprising: cresolricinoleicacid.

12. An emulsifiable insecticide comprising an addition product of amono-hydroxylic benzene derivative having its hydroxyi directly attachedto the benzene ring with an unsaturated fatty acid. A3. An emulsifiable011 comprising: a hydrocarbon oi1 containing from about 0.1% to 1.0% ofits volume of an addition product of a monohydroxylic benzene derivativehaving its hydroxyi directly attached to the benzene ring with anunsaturated fatty acid. 1

14. An emulsifiable oil comprising: a hydrocarbon oil containing fromabout 0.5% to 5.0% of its volume of an addition product of amonohydroxylio benzene derivative having its hydroxyl directly attachedto the benzene ring with an unsaturated acid.

ARTHUR G. KA.

